201202377 六、發明說明： 【發明所屬之技術領域】 本發明係關於黏著劑組成物及電路構件之連接構造。 【先前技術】 於半導體兀件及液晶顯示元件，爲了結合元件中的各 種構件之目的’自先前技術以來使用各種黏著劑，要求黏 著劑需具備的特性，從黏著性起，廣至耐熱性、高溫高濕 狀態之信頼性等多方面。此外，作爲被黏著的被黏著物， 以印刷電路板或聚醯亞胺等之有機基材爲主，及可使用具 有銅、鋁等金屬或ITO、SiNx、Si02等之各式各樣的表面 狀態之基材’因此，黏著劑必須具有配合各黏著物之分子 設計。 先前技術，作爲半導體元件或液晶顯示元件用的黏著 劑’使用具有優異的黏著性、且顯示出高信賴性之環氧樹 脂等之熱硬化性樹脂（例如，參考專利文獻1)。此黏著劑 的構成成份，一般使用環氧樹脂、與環氧樹脂具有反應性 之苯酚樹脂等之硬化劑、促進環氧樹脂與硬化劑反應之潛 熱性觸媒；潛熱性觸媒係決定黏著劑的硬化溫度及硬化速 度之重要因子，由在室溫的貯藏穩定性及加熱時的硬化速 度的觀點而言，使用各種的化合物。該相關構成的黏著劑 ，在實際的步驟係藉由以170〜2 50°C的溫度加熱1〜3小時 而硬化’而得到所希望的黏著。 惟，近年來隨著半導體元件的高積體化、液晶元件的 201202377 高精密化，元件間及配線間的間隔朝向狹小化進行，而會 擔心因爲硬化時的加熱而對周邊構件造成壞影ϋ。而且爲 了低成本化’必須提高生產量，故要求低溫且短時間的硬 化，換言之’要求低溫速硬化之黏著。爲了達到此低溫速 硬化，有使用活性化能量低的潛熱性觸媒之方法，但己知 在此情況下，很難兼具有在室溫附近的貯藏穩定性。 最近，倂用丙烯酸酯衍生物或甲基丙烯酸酯衍生物等 之自由基聚合性化合物與自由基聚合起始劑的過氧化物之 自由基硬化型黏著劑受到注目，自由基硬化因爲其反應性 活性種之自由基富含反應性，故可短時間硬化（例如，參 考專利文獻2)，惟，自由基硬化系的黏著劑因爲硬化時的 硬化收縮大，故與使用環氧樹脂時比較下，了解到其黏著 強度差。因此，作爲黏著強度的改良方法，提議使用藉由 醚鍵賦予柔軟性及可撓性之尿烷丙烯酸酯化合物作爲自由 基聚合性化合物之方法（例如，參考專利文獻3、4)。 專利文獻1 :特開平0 1 1 3 4 8 0號公報 專利文獻2 :特開2 0 0 2 - 2 0 3 4 2 7號公報 專利文獻3 :特許第3 5 2 2 6 3 4號公報 專利文獻4 :特開2002-2 8 5 1 2 8號公報 【發明內容】 〔發明所欲解決之課題〕 惟，使用上述尿烷丙烯酸酯時，因爲分子內具有醚鍵 ，而產生硬化後的彈性率或玻璃轉移溫度等的黏著劑物性 -6- 201202377 降低’而且吸水率上昇或耐水解性降低等問題。因此，使 用於要求在高溫高濕條件（例如85 °C /85 %RH)中長時間的 曝露（高溫高濕試驗）後亦具有穩定的性能之半導體元件或 液晶顯示元件的黏著劑時，信賴性試驗後黏著力或連接電 阻等的特性惡化。 因此本發明係鑑於上述先前技術所具有的問題所完成 者，其目的係提供可得到優異的黏著強度，而且即使信賴 性試驗（高溫高濕試驗）後仍可維持穩定的性能（黏著強度及 連接電阻）之黏著劑組成物及電路構件之連接構造。 〔用以解決課題之手段〕 爲了達成上述目的，本發明提供一種含有（a)熱塑性樹 脂、與（b)分子內具有1個以上的芴構造之自由基聚合性化 合物、與（c)自由基聚合起始劑之黏著劑組成物。 本發明的黏著劑組成物，係含有自由基聚合性化合物 、與自由基聚合起始劑之所謂的自由基硬化型黏著劑組成 物。認爲本發明的黏著劑組成物，因爲於自由基硬化型黏 著劑組成物中含有作爲自由基聚合性化合物之（b)分子內具 有1個以上的芴構造之自由基聚合性化合物，故硬化收縮 被降低而可得到優異的黏著強度，同時藉由硬化物的耐熱 性的提升，而即使在信賴性試驗（高溫高濕試驗）後亦可維 持優異的特性，此外，藉由剛直的芴骨架提高硬化物物性 (彈性率），而更提高信賴性。如上述，本發明的黏著劑組 成物因爲顯示出優異的黏著強度，而且信賴性試驗後亦可 201202377 維持穏定的性能，故適合作爲電路連接材料使用。 此外，本發明的黏著劑組成物再含有（d)分子內具有1 個以上的磷酸基之乙烯化合物較佳，因爲含有該（d)分子內 具有至少1個以上的磷酸基之乙烯化合物，黏著劑組成物 可得到與各式各樣的基材，特別是金屬等之優異的黏著強 度。 此外，本發明的黏著劑組成物中，上述（a)熱塑性樹脂 ’較佳爲含有至少一種選自苯氧基樹脂、聚酯樹脂、聚尿 烷樹脂、聚酯尿烷樹脂、丁縮醛樹脂、丙烯酸樹脂、及聚 醯亞胺樹脂所成之群。藉由使用該（a)熱塑性樹脂，黏著劑 組成物係因爲耐熱性及黏著性的提高，可得到優異的黏著 強度，同時因爲硬化物的耐熱性的提高，即使在信賴性試 驗（高溫高濕試驗）後亦可維持優異的特性。 此外，本發明的黏著劑組成物，再含有（e)導電性粒子 更佳，因爲藉由使其含有（e)導電性粒子，黏著劑組成物可 被賦予導電性或各向異導電性，使黏著劑組成物可適用於 具有電路電極之電路構件彼此的連接用途等。 本發明亦提供一種電路構件之連接構造，其係具備： 第一電路基板的主面上形成有第一電路電極之第一電路構 件、及第二電路基板的主面上形成有第二電路電極之第二 電路構件、及被設置在上述第一電路基板的主面與上述第 二憊路驻板的主面之間，使上述第一電路電極與上述第二 電路電極在對向配置狀態下連接上述第一及第二電路構件 彼此的電路連接構件之電路構件之連接構造；上述電路連 201202377 接構件係由上述本發明的黏著劑組成物的硬化物所成，使 對向的上述第一電路電極與上述第二電路電極進行電連接。 該電路構件之連接構造中，因爲第一及第二電路構件 彼此藉由上述本發明的黏著劑組成物的硬化物所成的電路 連接構件進行連接，可充分的提高電路構件彼此的黏著強 度，而且，即使在信賴性試驗（高溫高濕試驗）後亦可維持 穩定的性能（黏著強度或連接電阻）。 〔發明之效果〕 依據本發明，可提供雖爲自由基硬化系，但可得到優 異的黏著強度，而且即使在信賴性試驗（例如85°C /85%RH 放置）後亦可維持穩定的性能（黏著強度或連接電阻）之黏著 劑組成物及電路構件之連接構造。 〔實施發明之最佳形態〕 以下，依情況參考圖面詳細說明關於本發明的最適實 施形態，再者，圖面中，同一或相當的部份附有同一符號 ，省略重複的說明。此外，以下的說明中，（甲基）丙烯酸 意謂丙烯酸或與其對應的甲基丙烯酸；（甲基）丙烯酸酯意 謂丙烯酸酯或與其對應的甲基丙烯酸酯；（甲基）丙烯醯基 意謂丙烯醯基或與其對應的甲基丙烯醯基。 本發明的黏著劑組成物其特徵係含有（a)熱塑性樹脂、 與（b)分子內具有1個以上的芴構造之自由基聚合性化合物 、與（c)自由基聚合起始劑。 -9- 201202377 本發明中所使用的（a)熱塑性樹脂，並沒有特別的限制 ，可使用習知之物，可使用例如聚醯亞胺、聚醯胺、苯氧 基樹脂類、聚（甲基）丙烯酸酯、聚醯亞胺類、聚尿烷類、 聚酯類、聚酯尿烷類、聚乙烯丁縮醛類等；此外，由黏著 強度的觀點而言，（a)熱塑性樹脂較佳爲使用至少一種選自 苯氧基樹脂、聚酯樹脂、聚尿烷樹脂、聚酯尿烷樹脂、丁 縮醛樹脂、丙烯酸樹脂、及聚醯亞胺樹脂所成之群，此等 可使用單獨一種或混合2種以上使用。而且，此等樹脂係 分子內可含有矽氧烷鍵或氟取代基，混合2種以上此等的 熱塑性樹脂使用時，較適用者爲所混合的樹脂彼此完全相 溶，或者產生微相分離而成白濁狀態之樹脂。 本發明的黏著劑組成物，係所使用的（a)熱塑性樹脂的 分子量愈大薄膜形成性愈優異，此外，可將影锣作爲黏著 劑組成物的流動性之熔融黏度設定在廣泛範圍內。（a)熱塑 性樹脂的分子S並沒特別的限制，一般的重量平均分子量 較佳爲5,000~150,000，特別佳爲10,000〜80,00()，重量平 均分子Μ未達5,000，則會有薄膜形成性劣化的傾向，超 過1 50, 〇〇〇則會有與其他的成份的相溶性降低之傾向。 於本發明的黏著劑組成物中，（a)熱塑性樹脂的含量， 以黏著劑組成物總Μ爲基準，較佳爲1 0〜80質量％，更佳 爲1 5〜7 0質量％，此含量未達1 0質量％則會有黏著性降俾 的傾向，超過8 0質S %則會有樹脂的流動性降低之傾向。 本發明中所使用的（b)自由基聚合性化合物，係分子內 具有1個以上的芴構造者，此外，（b)自由基聚合性化合物 -10- 201202377 ，由更提高耐熱性及黏著性之觀點而言，更佳爲分子內具 有2個以上從自由基聚合性之（甲基）丙烯醯基、乙烯基及 烯丙基所選的至少1種的基之化合物。 (b)自由基聚合性化合物’具體而言可列舉雙苯氧基乙 醇芴丙烯酸酯、雙酚芴二環氧丙基醚的環氧丙基上加成（ 甲基）丙烯酸之環氧（甲基）丙烯酸酯、雙酚芴二環氧丙基醚 的環氧丙基上加成乙二醇或丙二醇之化合物上導入（甲基） 丙稀釀基氧基之化合物、及下述一般式（A)、（B)所表示的 化合物等。此等中由可得到更優異的黏著強度且於信賴性 試驗後亦更充分的維持穩定的性能而言，較佳爲下述一般 式（A)所表示的化合物’此等化合物可單獨使用或混合2 種以上使用。 [化1]201202377 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a connection structure of an adhesive composition and a circuit member. [Prior Art] For semiconductor components and liquid crystal display elements, in order to combine various components in the components, various adhesives have been used since the prior art, and the adhesives are required to have properties ranging from adhesion to heat resistance. The reliability of high temperature and high humidity conditions and many other aspects. In addition, as an adherend to be adhered, an organic substrate such as a printed circuit board or a polyimide may be used, and a variety of surfaces such as copper, aluminum, or the like, or ITO, SiNx, SiO 2 or the like may be used. The substrate of the state 'Therefore, the adhesive must have a molecular design that matches the various adhesives. In the prior art, a thermosetting resin such as an epoxy resin which has excellent adhesion and exhibits high reliability is used as an adhesive for a semiconductor element or a liquid crystal display element (for example, refer to Patent Document 1). As a constituent component of the adhesive, an epoxy resin, a hardener such as a phenol resin reactive with an epoxy resin, a latent heat catalyst which promotes reaction between an epoxy resin and a hardener, and a latent heat catalyst determine an adhesive. The important factors of the hardening temperature and the hardening speed are various compounds from the viewpoints of storage stability at room temperature and curing speed at the time of heating. The adhesive of the related structure is cured in the actual step by heating at a temperature of 170 to 2 50 ° C for 1 to 3 hours to obtain a desired adhesion. However, in recent years, with the high integration of semiconductor elements and the high precision of 201202377 of liquid crystal elements, the interval between components and wirings has been narrowed, and there is a concern that peripheral components may be adversely affected by heating during hardening. . Further, in order to reduce the cost, it is necessary to increase the throughput, so that it is required to be hardened at a low temperature for a short period of time, in other words, it is required to adhere at a low temperature. In order to achieve such low-temperature-speed hardening, there is a method of using a latent heat catalyst having a low activation energy, but it is known that in this case, it is difficult to have storage stability at around room temperature. Recently, a radical-curable adhesive using a radically polymerizable compound such as an acrylate derivative or a methacrylate derivative and a radical polymerization initiator has been attracting attention, and radical sclerosis is due to its reactivity. Since the radical of the active species is highly reactive, it can be hardened for a short period of time (for example, refer to Patent Document 2), but the adhesive of the radical hardening type has a large hardening shrinkage upon hardening, so compared with the case of using an epoxy resin , learned that its adhesion strength is poor. Therefore, as a method for improving the adhesion strength, a method of imparting flexibility and flexibility of a urethane acrylate compound as a radical polymerizable compound by an ether bond has been proposed (for example, refer to Patent Documents 3 and 4). Patent Document 1: JP-A No. 0 1 1 3 4 8 No. Patent Document 2: JP-A-N02- 2 0 3 4 2 Patent Document 3: Patent No. 3 5 2 2 6 3 4 [Problem to be solved by the invention] However, when the urethane acrylate is used, since the molecule has an ether bond, the elasticity after hardening occurs. Adhesive properties such as rate or glass transition temperature -6 - 201202377 Reduced 'and increased water absorption rate or reduced hydrolysis resistance. Therefore, when it is used for an adhesive for a semiconductor element or a liquid crystal display element which requires stable performance after prolonged exposure (high temperature and high humidity test) in high temperature and high humidity conditions (for example, 85 ° C / 85% RH), After the sex test, the characteristics of adhesion or connection resistance deteriorated. Therefore, the present invention has been made in view of the problems of the prior art described above, and its object is to provide excellent adhesion strength, and to maintain stable performance even after a reliability test (high temperature and high humidity test) (adhesive strength and connection) The connection structure of the adhesive composition and the circuit member of the resistor). [Means for Solving the Problems] In order to achieve the above object, the present invention provides a radical polymerizable compound containing (a) a thermoplastic resin and (b) having one or more fluorene structures in a molecule, and (c) a radical. An adhesive composition of a polymerization initiator. The adhesive composition of the present invention is a so-called radical hardening type adhesive composition containing a radical polymerizable compound and a radical polymerization initiator. It is considered that the adhesive composition of the present invention contains a radically polymerizable compound (b) a radical polymerizable compound having one or more fluorene structures in the molecule, and is hardened in the radical-curable adhesive composition. The shrinkage is lowered to obtain excellent adhesion strength, and at the same time, the heat resistance of the cured product is improved, and excellent characteristics can be maintained even after the reliability test (high temperature and high humidity test), and further, the rigid skeleton is maintained. Improve the physical properties (elasticity) of the hardened material, and improve the reliability. As described above, the adhesive composition of the present invention is suitable for use as a circuit connecting material because it exhibits excellent adhesive strength and can maintain its stable performance after the reliability test. Further, the adhesive composition of the present invention further contains (d) an ethylene compound having one or more phosphate groups in the molecule, and the ethylene compound having at least one or more phosphate groups in the (d) molecule is adhered thereto. The composition of the agent provides excellent adhesion strength to a wide variety of substrates, particularly metals. Further, in the adhesive composition of the present invention, the (a) thermoplastic resin ' preferably contains at least one selected from the group consisting of a phenoxy resin, a polyester resin, a polyurethane resin, a polyester urethane resin, and a butyral resin. A group of acrylic resins and polyimide resins. By using the (a) thermoplastic resin, the adhesive composition can obtain excellent adhesion strength due to improvement in heat resistance and adhesion, and at the same time, because of the heat resistance of the cured product, even in the reliability test (high temperature and high humidity) Excellent properties can also be maintained after the test). Further, the adhesive composition of the present invention further contains (e) conductive particles, because by containing (e) conductive particles, the adhesive composition can be imparted with conductivity or isotropic conductivity. The adhesive composition can be applied to a connection use or the like of circuit members having circuit electrodes. The present invention also provides a connection structure for a circuit member, comprising: a first circuit member having a first circuit electrode formed on a main surface of the first circuit substrate; and a second circuit electrode formed on a main surface of the second circuit substrate And the second circuit member is disposed between the main surface of the first circuit board and the main surface of the second circuit board, and the first circuit electrode and the second circuit electrode are disposed in an opposite direction a connection structure of circuit members connecting the circuit connecting members of the first and second circuit members; wherein the circuit connection 201202377 is formed by the hardened material of the adhesive composition of the present invention to make the first of the first The circuit electrode is electrically connected to the second circuit electrode. In the connection structure of the circuit member, since the first and second circuit members are connected to each other by the circuit connecting member formed by the hardened material of the above-described adhesive composition of the present invention, the adhesion strength between the circuit members can be sufficiently improved. Moreover, stable performance (adhesive strength or connection resistance) can be maintained even after the reliability test (high temperature and high humidity test). [Effects of the Invention] According to the present invention, it is possible to provide a radical curing system, but excellent adhesion strength can be obtained, and stable performance can be maintained even after a reliability test (for example, at 85 ° C / 85% RH) (adhesive strength or connection resistance) of the adhesive composition and the connection structure of the circuit member. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail with reference to the drawings, and the same or equivalent parts will be denoted by the same reference numerals, and the repeated description will be omitted. Further, in the following description, (meth)acrylic acid means acrylic acid or methacrylic acid corresponding thereto; (meth)acrylic acid ester means acrylate or methacrylate corresponding thereto; (meth)acrylic acid It is an acryl fluorenyl group or a corresponding methacryl fluorenyl group. The adhesive composition of the present invention is characterized by comprising (a) a thermoplastic resin, (b) a radical polymerizable compound having one or more fluorene structures in the molecule, and (c) a radical polymerization initiator. -9- 201202377 The (a) thermoplastic resin used in the present invention is not particularly limited, and conventional materials can be used, and for example, polyimine, polyamine, phenoxy resin, poly(methyl) can be used. Acrylate, polyimine, polyurethane, polyester, polyester urethane, polyvinyl butyral, etc. Further, (a) thermoplastic resin is preferred from the viewpoint of adhesion strength In order to use at least one selected from the group consisting of a phenoxy resin, a polyester resin, a polyurethane resin, a polyester urethane resin, a butyral resin, an acrylic resin, and a polyimide resin, these may be used alone. One type or a mixture of two or more types is used. Further, these resin-based molecules may contain a decane bond or a fluorine-substituted group, and when two or more kinds of thermoplastic resins are used in combination, the resin to be mixed may be completely compatible with each other or may be microphase-separated. A resin in a white turbid state. In the adhesive composition of the present invention, the higher the molecular weight of the (a) thermoplastic resin, the more excellent the film formability, and the melt viscosity of the fluidity of the adhesive composition as a binder composition can be set in a wide range. (a) The molecule S of the thermoplastic resin is not particularly limited, and a general weight average molecular weight is preferably 5,000 to 150,000, particularly preferably 10,000 to 80,00 (), and the weight average molecular weight is less than 5,000, and film formation is possible. The tendency to deteriorate is more than 1 50, and the compatibility with other components tends to decrease. In the adhesive composition of the present invention, the content of the (a) thermoplastic resin is preferably from 10 to 80% by mass, more preferably from 1 5 to 70% by mass based on the total mass of the adhesive composition. When the content is less than 10% by mass, the adhesive tends to be lowered, and if it exceeds 80%, the fluidity of the resin tends to decrease. The (b) radically polymerizable compound used in the present invention has one or more ruthenium structures in the molecule, and (b) the radical polymerizable compound -10-20122377 improves heat resistance and adhesion. In view of the above, a compound having at least one selected from the group consisting of a radically polymerizable (meth)acryl fluorenyl group, a vinyl group, and an allyl group is more preferable. (b) a radically polymerizable compound 'specifically, a epoxy group of a bisphenoxyethanol oxime acrylate or a bisphenol fluorene diglycidyl ether (meth)acrylic acid (A) a compound in which a (meth) acryloyloxy group is introduced onto a compound in which a propylene group or a bisphenol quinone epoxidized propyl ether is added to a compound of ethylene glycol or propylene glycol, and the following general formula ( A), a compound represented by (B), and the like. In the above, in order to obtain more excellent adhesive strength and to maintain more stable stability after the reliability test, the compound represented by the following general formula (A) is preferably used. These compounds may be used alone or Mix 2 or more types. [Chemical 1]
上述式（A)中，R1及R2各自獨立地表示氫原子或甲基 ，k及1各自獨立地表示1~8的整數，再者，式（A)中，R1 彼此及R2彼此可各自相同或相異；此外，從更充分的得 到藉由芴構造所產生的剛直性的效果的觀點而言，k及1 各自獨立地表示4以下的整數較佳，3以下的整數更佳。 -11 - 201202377 [化2]In the above formula (A), R1 and R2 each independently represent a hydrogen atom or a methyl group, and k and 1 each independently represent an integer of 1 to 8, and further, in the formula (A), R1 and R2 may be the same as each other. In addition, from the viewpoint of more sufficiently obtaining the effect of the rigidity due to the 芴 structure, k and 1 each independently represent an integer of 4 or less, and an integer of 3 or less is more preferable. -11 - 201202377 [Chemical 2]
上述式（B)中，R3及R4各自獨立地表示氫原子或甲基 ，《1及η各自獨立地表示卜8的整數，再者，式（B)中， R3彼此及R4彼此可各自相同或相異；此外，從更充分的 得到藉由芴構造所產生的剛直性的效果的觀點而言，m及 η各自獨立地表示4以下的整數較佳，3以下的整數更佳 〇 (b)自由基聚合性化合物，如上述—般式（Α)及（Β)所表 不的化合物的2官能的化合物，比4官能等之化合物更佳 。使其含有如上述一般式（Α)及（Β)所表示的化合物之2官 能的化合物’比含有4官能的化合物更能適度的調整硬化 物的硬度，有效的提高黏著力。 本發明的黏著劑組成物中，（b)自由基聚合性化合物的 含量’係相對於1 〇〇質量份之（a)熱塑性樹脂，較佳爲 30〜250質量份，更佳爲50〜150質量份。此含量未達30 質量份時，則會有硬化後的耐熱性降低的疑慮，超過2 5 0 質量份，則作爲薄膜使用時，會有薄膜成形性降低的疑慮 〇 本發明中所使用的（C)自由基聚合起始劑，可使用從先 前技術既知的過氧化物或偶氮基化合物等之習知的化合物 -12- 201202377 ’再者’由穩定性、反應性及相溶性優良之觀點而言，（c) 自由基聚合起始劑，較佳爲使用1分鐘半衰期溫度爲 90〜175 °C，而且分子量爲180〜1,000之過氧化物爲佳，此 處之「1分鐘半衰期溫度」之意，係指使半衰期成爲1分 鐘的溫度，「半.衰期」之意係指化合物的濃度減少至初期 値的一半爲止的時間。 (c)自由基聚合起始劑，具體而言可列舉l，l，3,3-四甲 基丁基過氧化新癸酸酯、二（4-1-丁基環己基）過氧化二碳 酸醋、一（2-t -乙基己基）過氧化二碳酸醋、枯燃基過氧化 新癸酸酯、1，1 , 3，3 -四甲基丁基過氧化新癸酸酯、二月桂 醯基過氧化物、1 -環己基· 1 -甲基乙基過氧化新癸酸酯、t -己基過氧化新癸酸酯、t-丁基過氧化新癸酸酯、t-丁基過 氧化三甲基乙酸酯、1,1，3,3-四甲基丁基過氧化-2-乙基己 酸酯、2,5-二甲基-2,5-二（2-乙基己醯基過氧化）己烷、t-己 基過氧化-2-乙基己酸酯、t-丁基過氧化-2-乙基己酸酯、t-丁基過氧化新庚酸酯、卜戊基過氧化-2-乙基己酸酯、二-t-丁基過氧化六氫對苯二甲酸酯、t-戊基過氧化-3,5,5-三甲 基己酸酯、3 -羥基-1，1-二甲基丁基過氧化新癸酸酯' 1，1,3,3-四甲基丁基過氧化-2-乙基己酸酯、t-戊基過氧化 新癸酸酯、t-戊基過氧化-2-乙基己酸酯、二（3-甲基苯甲醯 基）過氧化物、二苯甲醯基過氧化物、二（4-甲基苯甲醯基） 過氧化物、2,2’-偶氮基雙- 2,4-二甲基戊腈、1,1 偶氮基 雙（1-乙醯氧基-1-苯基乙烷）、2,2，-偶氮基雙異丁腈、2,2’-偶氮基雙（2-甲基丁腈）、二甲基-2,2’·偶氮基雙異丁腈、 -13- 201202377 4,4’-偶氮基雙（4-氛基纈草酸）、1，1’-偶氮基雙（1-環己烷腈 )、t-己基過氧化異丙基單碳酸酯、t-丁基過氧化馬來酸' t-丁基過氧化-3,5,5-三甲基己酸酯、t-丁基過氧化月桂酸 酯、2,5-二甲基·2,5-二（3-甲基苯甲醯基過氧化）己烷、t-丁 基過氧化-2-乙甚己基單碳酸酯、t-己基過氧化苯甲酸酯、 2,5-二甲基-2,5-二（苯甲醯基過氧化）己烷、t-丁基過氧化 苯甲酸酯、二丁基過氧化三甲基己二酸酯、t-戊基過氧化 正辛酸酯、t-戊基過氧化異壬酸酯、t-戊基過氧化苯甲酸 酯等，此等化合物可單獨使用1種，亦可混合2種以上使 用。 此外，本發明中之（c)自由基聚合起始劑，可使用藉由 15 0〜7 5 0 nm的光照射而產生自由基之化合物，如此的化合 物並沒有特別的限制，可使用習知的化合物，藉由波長 15 0〜75 0 nm的光照射產生自由基之（c)自由基聚合起始劑， 例如 Photoinitiation, Photopolymerization, and Photocuring, J . - P . Fouassier, Hanser P u b 1 i s h e r s ( 1 9 9 5 年） 、pi 7~p35中所記載的a -乙醯胺基苯酮衍生物或膦氧化物 ，因爲對於光照射之敏感度高故較佳。此等的化合物可單 獨使用1種之外，亦可混合2種以上，或與上述過氧化物 或偶氮茲化合物混合後使用。 本發明的黏著劑組成物中，（〇自由基聚合起始劑的含 显，係相對於1 〇〇質量份之（a)熱塑性樹脂，較佳爲 0.1〜50質量份，更佳爲1〜30質量份。此含量未達0.1質 量份時，則會存硬化不足的疑慮，超過50質量份時，則 -14 - 201202377 會有放置穩定性降低的疑慮。 本發明中必要時可使用之（d)分子內具有 酸基之乙稀化合物’並沒有特別的限制，可 ’但較佳爲使用下述一般式（1)〜（3 )所表示的 ’本發明中之「乙烯化合物」之意，係包括 醯基之化合物。 [化3] 1個以上的磷 使用習知之物 化合物，再者 具有甲基丙烯In the above formula (B), R3 and R4 each independently represent a hydrogen atom or a methyl group, and "1 and η each independently represent an integer of Bu8, and in the formula (B), R3 and R4 may each be the same. In addition, from the viewpoint of more sufficiently obtaining the effect of the rigidity due to the 芴 structure, m and η each independently represent an integer of 4 or less, and an integer of 3 or less is more preferable (b) The radically polymerizable compound, such as the bifunctional compound of the compound represented by the above formula (Α) and (Β), is more preferable than the compound of tetrafunctional or the like. The compound which contains the compound of the compound represented by the above general formula (Α) and (Β) can adjust the hardness of the hardener more appropriately than the tetrafunctional compound, and the adhesion is effectively improved. In the adhesive composition of the present invention, the content of the (b) radical polymerizable compound is preferably from 30 to 250 parts by mass, more preferably from 50 to 150, per part by mass of the (a) thermoplastic resin. Parts by mass. When the content is less than 30 parts by mass, there is a concern that the heat resistance after curing is lowered. When the amount is more than 250 parts by mass, the film formability may be lowered when used as a film, which is used in the present invention ( C) a radical polymerization initiator, which can be used as a conventional compound known from the prior art, such as a peroxide or an azo compound, and the like, which is excellent in stability, reactivity, and compatibility. In the case of (c) a radical polymerization initiator, it is preferred to use a peroxide having a one-minute half-life temperature of 90 to 175 ° C and a molecular weight of 180 to 1,000, and a "one minute half-life temperature" herein. The meaning is the temperature at which the half-life is 1 minute, and the "half-life" means the time until the concentration of the compound is reduced to half of the initial enthalpy. (c) a radical polymerization initiator, specifically, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, bis(4-1-butylcyclohexyl)peroxydicarbonate Vinegar, mono(2-t-ethylhexyl)peroxydicarbonate, dry-burning peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, dilaurin Mercapto peroxide, 1-cyclohexyl·1-methylethyl peroxy neodecanoate, t-hexylperoxy neodecanoate, t-butyl peroxy neodecanoate, t-butyl Trimethylacetate oxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethyl Hexyl-based peroxy)hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butyl peroxy neoheptanoate, Pentylperoxy-2-ethylhexanoate, di-t-butylperoxy hexahydroterephthalate, t-pentylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxy neodecanoate 1, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-pentyl peroxidation Neodecanoate, t-pentyl peroxy 2-ethylhexanoate, bis(3-methylbenzylidene) peroxide, benzhydryl peroxide, bis(4-methylbenzhydryl) peroxide, 2, 2'-Azobis- 2,4-dimethylvaleronitrile, 1,1 azobis(1-ethenyloxy-1-phenylethane), 2,2,-azobis Isobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyronitrile, -13- 201202377 4,4'-azo Bis-(4-arylshikimate), 1,1'-azobis(1-cyclohexanecarbonitrile), t-hexylperoxyisopropylmonocarbonate, t-butylperoxymaleic acid 't-butyl peroxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis(3-methylbenzene Mercapto peroxy)hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzene Methyl hydrazide peroxy) hexane, t-butyl peroxybenzoate, dibutyl peroxydicarbon adipate, t-pentyl peroxyoctanoate, t-pentyl peroxidation Isodecanoate, t-pentyl peroxybenzoate, etc. May be used singly, two kinds or more thereof may be used. Further, in the (c) radical polymerization initiator of the present invention, a compound which generates a radical by irradiation with light of 15 0 to 75 nm may be used, and such a compound is not particularly limited, and a conventional one may be used. a compound that generates a radical (c) radical polymerization initiator by irradiation of light having a wavelength of 15 0 to 75 nm, such as Photoinitiation, Photopolymerization, and Photocuring, J. - P . Fouassier, Hanser P ub 1 ishers ( The a-acetyl benzophenone derivative or the phosphine oxide described in pi 7 to p35 is preferred because it is highly sensitive to light irradiation. These compounds may be used singly or in combination of two or more kinds thereof, or may be used in combination with the above-mentioned peroxide or azo compound. In the adhesive composition of the present invention, (the content of the ruthenium radical polymerization initiator is preferably 0.1 to 50 parts by mass, more preferably 1 to 1 part by mass per part by mass of the (a) thermoplastic resin. 30 parts by mass. When the content is less than 0.1 part by mass, there is a concern that the hardening is insufficient. When the amount is more than 50 parts by mass, the -14 to 201202377 may have a problem of lowering the stability of the placement. d) The ethylene compound having an acid group in the molecule is not particularly limited, but it is preferable to use the meaning of the "ethylene compound" in the present invention represented by the following general formulas (1) to (3). , which is a compound containing a mercapto group. [Chemical 3] One or more kinds of phosphorus are compounded with a conventional compound, and further, there is a methacrylic compound.
(1) OH(1) OH
[式（1)中，R5表示（甲基）丙烯醯基，r6表示 ’ w及X各自獨立地表示的整數，再者 彼此、R6彼此' w彼此及x彼此可各自相同 氫原子或甲基 ，式（1 )中，R5 或相異。] [化4] r 〇十2计〇4十h2 0 II / \ II )—P— [5ζ(2)Φ ’ R7表示（甲基）丙稀醯基，y及z 不1〜8的整數，再者，式（2)中，r7彼此、乂 可各自相同或相異。] (2) 各自獨立地表 彼此及Z彼此 -15- (3) (3)201202377 [化5][In the formula (1), R5 represents a (meth)acryl fluorenyl group, and r6 represents an integer represented by each of 'w and X, and further, each other, R6', and each other may each have the same hydrogen atom or methyl group. , in formula (1), R5 or different. ] [化4] r 〇10 2 〇 4 10 h2 0 II / \ II )—P— [5ζ(2)Φ ' R7 represents (meth) propyl sulfhydryl, y and z are not integers of 1 to 8 Further, in the formula (2), r7 may be the same or different from each other. (2) Each of them independently and each other and Z each other -15- (3) (3)201202377 [Chemical 5]
[式（3)中’ R8表示（甲莛）丙烯醯基，R9表示氫原子或甲基 ’ a及b各自獨立地表示1〜8的整數，再者，式（3)中，R9 彼此及a彼此可各自相同或相異。] (d)分子內具有1個以上的磷酸基之乙烯化合物，更具 體而言’可列舉磷酸基乙基甲基丙烯酸酯（acid phosphoxy ethyl methacrylate)、磷酸基乙基丙烯酸酯（acid phosphoxy ethyl acrylate)、磷酸蕋丙基甲基丙烯酸酯（acid phosphoxy propyl methacrylate)、磷酸基聚氧乙二醇單甲基丙烯酸酯 (acid phosphoxy polyoxyethylene glycol monomethacrylate)、磷酸基聚氧丙二醇單甲基丙烯酸醋 (acid phosphoxy ρο 1yoxypropy1ene glycol monomethacrylate) ' 2,2’-二（甲基）丙烯醯氧基二乙基磷酸 酯' E 0改性磷酸二甲基丙烯酸酯、磷酸改性環氧丙烯酸 酯、磷酸乙烯酯等。 本發明的黏著劑組成物中，（d)分子內具有1個以上的 磷酸基之乙烯化合物的含量，相對於5 0質量份之（a)熱塑 性樹脂，較佳爲0.1〜15質:g份，更佳爲0.5-10質量份， 此含fi未達〇 · 1質量份，則會有不易得到高黏著強度的傾 向，此外，超過1 5質量份，則易發生硬化後的黏著劑組 成物的物性降低，及信賴性降低的疑慮。 -16- 201202377 本發明中必要時所使用的（e)導電性粒子，可列舉例如 AU、Ag、Ni、Cu、焊接等之金屬粒子或碳粒子等。此外 ’（e)導電性粒子亦可爲以非導電性的玻璃、陶瓷、塑膠等 爲核，於此核上被覆上述金屬或金屬粒子、碳者，（e)導電 性粒子爲以塑膠爲核，於此核上被覆金屬或金屬粒子、碳 者’或爲熱熔融金屬粒子時，因爲加熱加壓時具有變形性 ’故在連接電路構件彼此時，增加導電性粒子與電極的接 觸面積而提高信賴性而較佳。此外，於此等的導電性粒子 的表面再用高分子樹脂等被覆的微粒子，抑制因爲增加導 電性粒子的摻合量時的粒子彼此的接觸所造成的短路，可 提高電路電極間的絕緣性。用高分子樹脂等被覆導電粒子 的表面之粒子，可單獨使用或與其他的導電性粒子混合使 用。 (e)導電性粒子的平均粒徑，由得到優良的分散性及導 電性的觀點而言，1〜1 8 μιη較佳。 此外，本發明的黏著劑組成物中的（e )導電性粒子的含 量，並沒特別的限制，以黏著劑組成物的總體積爲基準， 0.1〜30體積％較佳，更佳爲0.1〜10體積％。此含量未達 〇 . 1體積％，則會有導電性變差的傾向，超過3 0體積。/。， 則會有易使電路電極間發生短路之傾向。此外，（e)導電性 粒子的含量（體積％)，係決定於在23 °C時硬化前的各成份 的體積，再者，各成份的體積，可利用比重而將質量換算 成體積而計算得到，此外，在放進不會溶解、或膨潤此欲 測量體積之成份，而可充分地濕潤此成份的適當溶劑（水 -17- 201202377 、乙醇類等）之：s筒等中，於其中投進測量對象的成份， 可從所增加的體積計算此成份的體積。 此外’本發明的黏著劑組成物中亦可含有其他的自由 基聚合性化合物’與上述（b)分子內具有1個以上的芴構造 之自由基聚合性化合物倂用，如此的其他自由基聚合性化 合物’如苯乙烯衍生物或馬來酸酐縮亞胺衍生物，只要是 藉由自由基進行聚合之化合物即可，並沒有特別的限制， 可使用習知之物》 其他自由基聚合性化合物，具體而言可列舉環氧（甲 基）丙烯酸酯寡聚物、聚醚（甲基）丙烯酸酯寡聚物、及聚酯 (甲基）丙烯酸酯寡聚物等之寡聚物，以及三羥甲基丙烷三（ 甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、聚烷二醇二 (甲基）丙烯酸酯、二環戊烯基（甲基）丙烯酸酯、二環戊烯 氧基乙基（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、 二季戊四醇六（甲基）丙烯酸酯、三聚異氛酸改性2官能（甲 基）丙烯酸酯、及三聚異瓴酸改性3官能（甲基）丙烯酸酯等 之多官能（甲基）丙烯酸酯化合物。 此外’爲了調整黏著劑組成物的流動性，可使用單官 能（甲基）丙烯酸酯，單官能（甲基）丙烯酸酯可列舉例如季 戊四醇（甲基）丙烯酸酯、2 -氛基乙基（甲基）丙烯酸酯、環 己基（甲基）丙烯酸酯、二環戊烯（甲基）丙烯酸酯、二環戊 烯氧基乙基（甲基）丙烯酸酯、2-(2 -乙氧基乙氧基）乙基（甲 基）丙烯酸酯、2-乙氧基乙基（甲基）丙烯酸酯、2-乙基己基 (甲基）丙烯酸酯、η -己基（甲基）丙烯酸酯、2 -羥基乙基（甲 -18- 201202377 基）丙烯酸酯 '羥基丙基（甲基）丙烯酸酯、異冰片基（甲基） 丙烯酸酯、異癸基（甲基）丙烯酸酯、異辛基（甲基）丙烯酸 酯、η-月桂基（甲基）丙烯酸酯、2-甲氧基乙基（甲基）丙烯 酸酯、2 -苯氧基乙基（甲基）丙烯酸酯、四氫糠基（甲基）丙 烯酸酯、2-(甲基）丙烯醯氧基乙基磷酸酯、Ν,Ν-二甲基胺 基乙基（甲基）丙烯酸酯、Ν，Ν-二甲基胺基丙基（甲基）丙烯 酸酯、（甲基）丙烯醯基嗎啉。再者，此等的化合物單獨使 用1種以外，必要時可混合數種使用。 本發明的黏著劑組成物，爲了交聯率的提高之目的， 除了如上述的具有（甲基）丙烯醯基的化合物以外，亦可適 當地添加具有烯丙基 '馬來酸酐縮亞胺基、乙烯基等之可 藉由活性自由基進行聚合的官能基之化合物，該化合物具 體而言可列舉Ν-乙烯咪唑、Ν-乙烯吡啶、Ν-乙烯吡咯烷 酮、Ν -乙烯甲醯胺、Ν -乙烯己內醯胺、4,4’-乙烯叉雙 (Ν，Ν-二甲基苯胺）、Ν -乙烯乙醯胺、ν，Ν·二甲基丙烯醯胺 、Ν -異丙基丙烯醯胺、Ν,Ν -二乙基丙烯醯胺等。 本發明的黏著劑組成物中，以賦予硬化速度的控制或 貯藏穩定性爲目的’可添加穩定化劑，作爲如此的穩定化 劑’並沒有特別的限制，可使用習知之化合物，但較佳爲 本驅或氫醒等之酷衍生物、4 -甲氧基苯酣或4-t -丁基兒茶 酚等之苯酚衍生物、2,2,6,6-四甲基哌啶-1-羥基（oxyl)或 4-經基-2,2,6,6-四甲基哌π定-1-經基（〇xyi)等之胺經基 (aminoxyl)衍生物、四甲基哌啶基甲基丙烯酸酯等之受阻 胺衍生物。 -19- 201202377 穩定化劑的添加a，相對於1 〇〇質量份之（a)熱塑性樹 脂，較佳爲0.01〜30質量份，更佳爲〇·〇5〜10質量份，此 含量未達0.0 1質黛份時，會有不易得到充分的添加效果 的傾向，此外，超過3 0質ϋ份時，則會有與其他成份的 相溶性降低的傾向。 本發明的黏著劑組成物中，亦可添加代表烷氧基矽烷 衍生物或矽氮烷衍生物之偶合劑或密著提升劑、塗平劑等 之黏著輔助劑，作爲該黏著輔助劑，具體而言較佳爲下述 一般式（4)所表示的化合物，此等的黏著輔助劑可單獨使用 1種或混合2種以上使用。 [化6] 〒1〇 R11-Si—{CH2)-R13 (4) [式（4)中’ Rig、R11及R12各自獨立地表示氫原子、碳數 1〜5的烷基、碳數的烷氧基、碳數1〜5的烷氧基羰基 、或芳31 ’ R13表示（甲基）丙烯醯基、乙烯基、異瓿酸酯 基、咪唑基、锍基、胺基、甲基胺蕋、二甲基胺基、苄基 胺基、苯基胺基、環己基胺基、嗎啉基、哌啶基、脲基、 或環氧丙基，c表示1~1〇整數。] 本發明的黏著劑組成物中，以應力緩和及黏著性提高 爲目的，亦可添加橡膠成份，作爲橡膠成份具體而言可列 舉聚異戊二烯、聚丁二烯、羧基末端聚丁二烯、羥基末端 聚丁二烯、1，2 -聚丁二烯、羧基末端1，2 -聚丁二烯、羥基 -20- 201202377 末端1,2 -聚丁二烯、丙烯酸橡膠、苯乙烯-丁二烯橡膠、 羥基末端苯乙烯-丁二烯橡膠、丙烯腈-丁二烯橡膠、聚合 物末端含有羧基、羥基、（甲基）丙烯醯基或嗎啉基之丙烯 腈·丁二烯橡膠、羧基化腈橡膠、羥基末端聚（氧基丙烯）、 烷氧基矽烷基末端聚（氧基丙烯）、聚（氧基四伸甲基）甘醇 、聚烯烴甘醇、聚-ε -己內酯。 作爲上述橡膠成份，由黏著性提高的觀點而言，在側 鏈或末端含有局極性基之氰基、殘基之膠橡成份較佳，由 流動性更提高的觀點而言，液狀橡膠較佳。作爲橡膠成份 具體而言，可列舉液狀丙烯腈-丁二烯橡膠、聚合物末端 含有羧基、羥基、（甲基）丙烯醯基或嗎啉基之液狀丙烯腈-丁二烯橡膠、液狀羧化腈橡膠。此等橡膠成份中，極性基 之丙烯腈含量爲1 0~60質量％較佳，此等化合物可單獨使 用1種或混合2種以上使用。 本發明的黏著劑組成物’於室溫（〇〜3〇t )爲液狀時， 可以糊料狀使用’室溫〜30°C )下爲固體時，加熱後使用 以外，使用溶劑使其糊料化後使用亦可。此處，可使用的 溶劑，只要是與黏著劑組成物（亦含添加劑）無反應性，且 可充分的溶解黏著劑組成物者即可’並沒有特別的限制， 較佳爲常壓下的沸點爲5 〇〜1 5 〇 °c者，沸點未達5 0 t：時， 則放置於室溫（〇〜30 °C )會有揮發的疑慮，故在開放系統中 的使用受到限制’此外，沸點超過1 5 〇 °C，則溶劑很難揮 發’會有對黏著後的信賴性產生壞影響的疑慮。 本發明的黏著劑組成物’可形成薄膜狀後作爲薄膜狀 -21 - 201202377 黏著劑使用。在形成薄膜狀黏著劑時，可藉 組成物中必要時加入溶劑等所得到的溶液， 薄膜、聚對苯二甲酸乙二醇酯薄膜、脫膜紙 材上’或使不織布等基材含浸上述溶液後放 材上，去除溶劑等而形成薄膜狀。以薄膜狀 由操作性等的觀點而言更爲便利。 圖1係表示由本發明的黏著劑組成物所 著劑的其中之一實施形態之截面圖，圖1所 著劑1，爲使上述黏著劑組成物形成薄膜狀 此薄膜狀黏著劑，操作容易，容易被設置在 容易地進行連接作業。此外，薄膜狀黏著劑 2種以上的層所成的多層構成（未圖示）。 本發明的黏著劑組成物及薄膜狀黏著劑 加熱及加壓而使被黏著物彼此連接。加熱溫 的限制，但較佳爲100〜2 5 0 °c的溫度，壓力 被黏著物的範園即可，並沒有限制，一舟 0.1~10MPa，此等加熱及加壓，在0.5〜120 較佳。依據本發明的黏著劑組成物及薄膜狀 使用1 40〜200°C、3MPa的條件，即使1 0秒 熱及加壓亦可使被黏著物彼此充分的連接。 此外，本發明的黏著劑組成物及薄膜狀 爲熱膨脹係數不同之不同種類的被黏著物的 具體而Η，可作爲以各向異導電黏著劑，銀 代表的電路黏著材料，以CSP用彈性體 由將在黏著劑 塗佈於氟樹脂 等之剥離性基 置在剥離性基 黏膜劑使用， 成的薄膜狀黏 示的薄膜狀黏 所成者，依據 被黏著物，可 1，可具有由 ，通常可倂用 度並沒有特別 只要在不損及 乏而言較佳爲 秒的範園進行 黏著劑，例如 的短時間的加 黏著劑，可作 黏著劑使用， 裔、銀薄膜爲 C S Ρ用墊料 -22- 201202377 (Under Fill)材料、導線架之電子用膠帶（L〇CTape)爲代表 的半導體元件黏著材料使用。 & T ’將本發明的黏著劑組成物及薄膜狀黏著劑作爲 各向異導電性黏著劑組成物及各向異導電性薄膜使用，說 明關於連接在電路基板的主面上形成電路電極之電路構件 彼此時的其中之例，亦即，將各向異導電性黏著劑組成物 或各向異導電性薄膜，配置於電路基板上之相對的電路電 極間’藉由加熱加壓，進行對向的電路電極間的電連接與 電路基板間的黏著，可連接電路構件彼此。此處，作爲形 成電路電極的電路基板，可使用由半導體、玻璃、陶瓷等 之無機物所成的基板，聚醯亞胺、聚碳酸酯等之有機物所 成的基板，組合玻璃/環氧等之無機物與有機物之基板等 。此外，在作爲如此的電路連接材料的用途上使用本發明 的黏著劑組成物及薄膜狀黏著劑時，使此等中含有導電性 粒子較佳。 圖2係表示本發明的電路構件之連接構造的其中之一 的實施形態之槪略截面圖，如圖2所示，本實施形態的電 路構件之連接構造，具備互相對向之第一電路構件20及 第二電路構件30，第一電路構件20及第二電路構件30之 間，設置連接此等之電路連接構件1 〇。 第一電路構件20係具備電路基板（第一電路基板）21、 及形成於電路基板21的主面21a上之電路電極（第一電路 電極）22。再者，電路基板21的主面21a上，依情況可形 成絕緣層（未圖不）。 -23- 201202377 另一方面，第二電路構件3 0係具備電路基板（第二電 路基板）3 1、及形成於電路基板3 1的主面3 1 a上之電路電 極（第二堪路電極）32。此外，電路基板3 1的主面3 1 a上， 依情況可形成絕緣層（未圖示）。 第一及第二電路構件20、3 0，只要是形成進行電連接 時所必須的電極者即可，並沒有特別的限制。具體而言， 可列舉在液晶顯示面板所使用的ITO等中形成電極之玻璃 或塑膠基板、印刷電路板、陶瓷配線板、可撓性配線板、 半導體矽晶片等。此等必要時可組合使用。像這樣，本實 施形態，可使用由印刷配線板及聚醯亞胺等之有機物所成 的材質爲代表，以及具有如銅、鋁等的金屬及ITO(indium tin oxide)、氮化矽（SiNx)、二氧化矽（Si02)等之無機材質 之各種各樣的表面狀態之電路構件。 電路連接構件1 〇，係由本發明的黏著劑組成物或薄膜 狀黏著劑的硬化物所成者，此電路連接構件I 〇，係含有絕 緣性物質π及導電性粒子7 :導電性粒子7 ’係不僅配置 於對向的電路電極22及電路電極3 2之間’亦配置於主面 2 1 a、3 1 a之間。電路構件之連接構造中，電路電極22、 3 2係隔著導電性粒子7進行電連接，亦即’導電性粒子7 與電路蜇極22、32雙方直接接觸。 此處，導電性粒子7爲之前所說明的（e)導電性粒子， 絶緣性物質Π爲構成本發明的黏著劑組成物或薄膜狀黏 著劑之絶緣性的各成份之硬化物。 此電路構件之連接構造中，如上述’對向的電路電極 -24- 201202377 2 2與電路電極3 2係隔著導電性粒子7進行電連接，因此 ，充分的降低電路電極22、32間的連接電阻，所以電路 電極22、32間的電流的流動可順利進行，可充分的發揮 電路所具有的功能。此外1電路連接構件未含有導電 性粒子7時，藉由使電路電極22及電路電極32直接接觸 而進行電連接。 電路連接構件1 0因爲由本發明的黏著劑組成物或薄 膜狀黏著劑的硬化物所構成，所以對於電路構件2 0或3 0 而目’電路連接構件10的連接強度充分的變高，而且， 即使信賴性試驗（高溫高濕試驗）後亦可維持穩定的性能（黏 者強度及連接電阻）。[In the formula (3), R 8 represents a (meth) acryl fluorenyl group, and R 9 represents a hydrogen atom or a methyl group ' a and b each independently represent an integer of 1 to 8, and further, in the formula (3), R 9 and a can be the same or different from each other. (d) A vinyl compound having one or more phosphate groups in the molecule, and more specifically, 'acid phosphoxy ethyl methacrylate, acid phosphoxy ethyl acrylate ), acid phosphoxy propyl methacrylate, acid phosphoxy polyoxyethylene glycol monomethacrylate, phosphate polyoxypropylene glycol monomethacrylate (acid phosphoxy) Οο 1yoxypropy1ene glycol monomethacrylate) '2,2'-bis(meth)acryloyloxydiethyl phosphate' E 0 modified phosphoric acid dimethacrylate, phosphoric acid modified epoxy acrylate, vinyl phosphate, and the like. In the adhesive composition of the present invention, (d) the content of the ethylene compound having one or more phosphate groups in the molecule is preferably 0.1 to 15 mass: g parts based on 50 parts by mass of the (a) thermoplastic resin. More preferably, it is 0.5 to 10 parts by mass, and if the content of fi is less than 1 part by mass, the adhesive strength tends to be difficult to obtain, and in addition, when it exceeds 15 parts by mass, the adhesive composition tends to be hardened. Reduced physical properties and doubts about reduced reliability. -16-201202377 The (e) conductive particles used in the present invention may, for example, be metal particles such as AU, Ag, Ni, Cu, or the like, or carbon particles. Further, the (e) conductive particles may be made of non-conductive glass, ceramics, plastics or the like, and the metal or metal particles or carbon may be coated on the core. (e) The conductive particles are made of plastic. When the metal or metal particles or the carbon particles are coated on the core, or the hot molten metal particles are deformed by heating and pressurization, when the circuit members are connected to each other, the contact area between the conductive particles and the electrodes is increased to improve. Trustworthy and better. In addition, the fine particles coated with the polymer resin or the like on the surface of the conductive particles suppress the short circuit caused by the contact between the particles when the amount of the conductive particles is increased, thereby improving the insulation between the circuit electrodes. . The particles coated on the surface of the conductive particles with a polymer resin or the like may be used alone or in combination with other conductive particles. (e) The average particle diameter of the conductive particles is preferably from 1 to 18 μm from the viewpoint of obtaining excellent dispersibility and conductivity. Further, the content of the (e) conductive particles in the adhesive composition of the present invention is not particularly limited, and is preferably 0.1 to 30% by volume, more preferably 0.1 to 10% based on the total volume of the adhesive composition. 10% by volume. If the content is less than 〇1% by volume, the conductivity tends to be deteriorated, and it exceeds 30% by volume. /. There is a tendency to cause a short circuit between the circuit electrodes. Further, (e) the content (% by volume) of the conductive particles is determined by the volume of each component before curing at 23 ° C, and the volume of each component can be calculated by converting the mass into a volume by using the specific gravity. In addition, in a suitable solvent (water-17-201202377, ethanol, etc.) which does not dissolve or swell the component to be measured, which can sufficiently wet the component: The component of the measurement object is injected, and the volume of the component can be calculated from the increased volume. Further, the "adhesive composition of the present invention may contain another radical polymerizable compound" and the above (b) a radically polymerizable compound having one or more fluorene structures in the molecule, such other radical polymerization The compound such as a styrene derivative or a maleic anhydride imide derivative is not particularly limited as long as it is a compound which is polymerized by a radical, and a conventional radical polymerizable compound can be used. Specific examples thereof include an epoxy (meth) acrylate oligomer, a polyether (meth) acrylate oligomer, and an oligomer such as a polyester (meth) acrylate oligomer, and trishydroxyl Methylpropane tri(meth)acrylate, polyethylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentan Alkenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimeric octa-acid modified bifunctional (meth) acrylate, And trimeric isophthalic acid modification A polyfunctional (meth) acrylate compound such as a trifunctional (meth) acrylate. Further, in order to adjust the fluidity of the adhesive composition, a monofunctional (meth) acrylate may be used, and a monofunctional (meth) acrylate may, for example, be pentaerythritol (meth) acrylate or 2-alkylethyl (A) Acrylate, cyclohexyl (meth) acrylate, dicyclopentene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-(2-ethoxy ethoxylate) Ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, η-hexyl (meth) acrylate, 2-hydroxyl Ethyl (methyl-18- 201202377) acrylate 'hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (methyl) Acrylate, η-lauryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroindenyl (methyl) Acrylate, 2-(meth)acryloyloxyethyl phosphate, hydrazine, hydrazine-dimethylaminoethyl (methyl Acrylate, hydrazine, hydrazine-dimethylaminopropyl (meth) acrylate, (meth) propylene hydrazinomorpholine. Further, these compounds may be used alone or in combination of several kinds as necessary. In order to improve the crosslinking ratio of the adhesive composition of the present invention, in addition to the above-mentioned compound having a (meth)acryl fluorenyl group, an allyl 'maleic anhydride imide group may be appropriately added. a compound of a functional group which can be polymerized by a living radical such as a vinyl group, and examples of the compound include fluorene-vinylimidazole, hydrazine-vinylpyridine, hydrazine-vinylpyrrolidone, fluorene-vinylformamide, hydrazine- Ethylene caprolactam, 4,4'-vinylidene bis(indole, decyl-dimethylaniline), hydrazine-ethylene acetamide, ν, Ν·dimethyl methacrylate, Ν-isopropyl propylene hydrazine Amine, hydrazine, hydrazine-diethyl acrylamide and the like. In the adhesive composition of the present invention, a stabilizer may be added for the purpose of imparting control of the curing rate or storage stability, and as such a stabilizer, there is no particular limitation, and a conventional compound may be used, but preferably. a cool derivative such as a hydrazine or hydrogen hydrazine, a phenol derivative such as 4-methoxyphenylhydrazine or 4-t-butylcatechol, 2,2,6,6-tetramethylpiperidine-1 -Aminol or 4-amino-2,2,6,6-tetramethylpiperidin-1-yl-based (aminoxy) derivatives such as aminoxyl derivatives, tetramethylpiperidine A hindered amine derivative such as a methacrylate. -19- 201202377 The addition of the stabilizer is preferably 0.01 to 30 parts by mass, more preferably 5 to 10 parts by mass, based on 1 part by mass of the (a) thermoplastic resin, and the content is not up to When 0.01 is used as a part, it tends to be difficult to obtain a sufficient effect of addition, and when it exceeds 30%, compatibility with other components tends to be lowered. In the adhesive composition of the present invention, a coupling agent representing an alkoxydecane derivative or a decazane derivative, or an adhesion aid such as a adhesion enhancer or a coating agent may be added as the adhesion aid. In the case of the above-mentioned general formula (4), the above-mentioned adhesion aids may be used alone or in combination of two or more. 〒1〇R11-Si—{CH2)-R13 (4) [In the formula (4), Rig, R11 and R12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon number. Alkoxy group, alkoxycarbonyl group having 1 to 5 carbon atoms, or aryl 31 ' R13 represents (meth)acryloyl group, vinyl group, isodecanoate group, imidazolyl group, fluorenyl group, amine group, methylamine An anthracene, a dimethylamino group, a benzylamino group, a phenylamino group, a cyclohexylamino group, a morpholinyl group, a piperidinyl group, a ureido group, or a glycidyl group, and c represents an integer of 1 to 1 Å. In the adhesive composition of the present invention, for the purpose of stress relaxation and adhesion improvement, a rubber component may be added. Specific examples of the rubber component include polyisoprene, polybutadiene, and carboxyl terminal polybutadiene. Alkene, hydroxyl terminated polybutadiene, 1,2-polybutadiene, carboxy terminal 1,2-polybutadiene, hydroxy-20- 201202377 terminal 1,2-polybutadiene, acrylic rubber, styrene - Butadiene rubber, hydroxyl terminated styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylonitrile butadiene rubber containing carboxyl group, hydroxyl group, (meth) acrylonitrile group or morpholinyl group at the polymer end , carboxylated nitrile rubber, hydroxyl-terminated poly(oxypropylene), alkoxyfluorenyl-terminated poly(oxypropylene), poly(oxytetramethyl)glycol, polyolefin glycol, poly-ε-hexyl Lactone. As the rubber component, from the viewpoint of improving the adhesion, the rubber component having a cyano group or a residue having a polar group at the side chain or the terminal is preferred, and from the viewpoint of higher fluidity, the liquid rubber is more preferable. good. Specific examples of the rubber component include liquid acrylonitrile-butadiene rubber, liquid acrylonitrile-butadiene rubber having a carboxyl group, a hydroxyl group, a (meth) acrylonitrile group or a morpholinyl group at the polymer terminal, and a liquid. Carboxylated nitrile rubber. In the rubber component, the acrylonitrile content of the polar group is preferably from 10 to 60% by mass, and these compounds may be used singly or in combination of two or more. When the adhesive composition of the present invention is liquid at room temperature (〇~3〇t), it can be used as a solid in the form of a paste at room temperature to 30 ° C, and it can be used with a solvent other than after heating. It can also be used after paste. Here, the solvent which can be used is not particularly limited as long as it is non-reactive with the adhesive composition (including an additive) and can sufficiently dissolve the adhesive composition, and is preferably under normal pressure. If the boiling point is 5 〇~1 5 〇°c, the boiling point is less than 50 t: when it is placed at room temperature (〇~30 °C), there is a doubt that it will be volatilized, so the use in open systems is limited. When the boiling point exceeds 15 〇 ° C, the solvent is difficult to volatilize, which may have a bad influence on the reliability after adhesion. The adhesive composition 'of the present invention' can be formed into a film shape and used as a film-like adhesive - 21 - 201202377. When a film-like adhesive is formed, a solution obtained by adding a solvent or the like to a composition, a film, a polyethylene terephthalate film, a release paper, or a substrate such as a nonwoven fabric may be impregnated. After the solution is placed on the material, the solvent or the like is removed to form a film. In the form of a film, it is more convenient from the viewpoint of workability and the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of an adhesive composition of the present invention, and the agent 1 of Fig. 1 is an easy-to-use operation for forming the film-like adhesive into a film-like adhesive composition. It is easy to set up in easy connection work. Further, a film-like adhesive has a multilayer structure of two or more layers (not shown). The adhesive composition of the present invention and the film-like adhesive are heated and pressurized to connect the adherends to each other. Heating temperature limit, but preferably 100~2 50 °c temperature, pressure can be adhered to the fan garden, there is no limit, a boat 0.1~10MPa, such heating and pressurization, in 0.5~120 Preferably. According to the adhesive composition and the film form of the present invention, the conditions of 1 40 to 200 ° C and 3 MPa can be used to sufficiently bond the adherends to each other even under heat and pressure for 10 seconds. Further, the adhesive composition and the film form of the present invention are specific types of different types of adherends having different thermal expansion coefficients, and can be used as a circuit adhesive material represented by an isotropic conductive adhesive, silver, and an elastomer for CSP. A film-like adhesive film which is formed by applying a release agent such as a fluororesin to a release-based base film, and which is formed by a film-like adhesive film, may have one or more depending on the adherend. Generally, the degree of usability is not particularly limited as long as the adhesive is preferably used in the form of a second, which is preferably a second, such as a short-term adhesive, which can be used as an adhesive, and the silver film is used for CS. Padding-22- 201202377 (Under Fill) material, wire holder electronic tape (L〇CTape) is used as a semiconductor component adhesive material. < T ' The adhesive composition and the film-like adhesive of the present invention are used as an isotropic conductive adhesive composition and an isotropic conductive film, and the formation of circuit electrodes on the main surface of the circuit substrate is described. In the case where the circuit components are mutually connected, that is, the oppositely-conductive adhesive composition or the isotropic conductive film is disposed between the opposing circuit electrodes on the circuit board by heating and pressurizing The electrical connection between the circuit electrodes and the adhesion between the circuit boards can be connected to the circuit members. Here, as the circuit board on which the circuit electrode is formed, a substrate made of an inorganic material such as a semiconductor, glass, or ceramic, a substrate made of an organic substance such as polyimide or polycarbonate, or a combination of glass/epoxy or the like can be used. A substrate of an inorganic substance and an organic substance. Further, when the adhesive composition of the present invention and the film-like adhesive are used for the use as such a circuit connecting material, it is preferable to contain conductive particles in these. 2 is a schematic cross-sectional view showing an embodiment of a connection structure of a circuit member according to the present invention, and as shown in FIG. 2, the connection structure of the circuit member of the present embodiment includes first circuit members opposed to each other. 20 and the second circuit member 30, between the first circuit member 20 and the second circuit member 30, a circuit connecting member 1 for connecting these is provided. The first circuit member 20 includes a circuit board (first circuit board) 21 and a circuit electrode (first circuit electrode) 22 formed on the main surface 21a of the circuit board 21. Further, an insulating layer (not shown) may be formed on the main surface 21a of the circuit board 21 as the case may be. -23-201202377 On the other hand, the second circuit member 30 includes a circuit board (second circuit board) 31 and circuit electrodes formed on the main surface 31a of the circuit board 31 (second electrode) ) 32. Further, an insulating layer (not shown) may be formed on the main surface 3 1 a of the circuit board 31 as the case may be. The first and second circuit members 20 and 30 are not particularly limited as long as they are electrodes necessary for electrical connection. Specifically, a glass or plastic substrate in which an electrode is formed in ITO or the like used in a liquid crystal display panel, a printed wiring board, a ceramic wiring board, a flexible wiring board, a semiconductor germanium wafer, or the like can be given. These can be used in combination if necessary. As described above, in the present embodiment, a material made of an organic material such as a printed wiring board or a polyimide may be used, and a metal such as copper or aluminum, ITO (indium tin oxide) or tantalum nitride (SiNx) may be used. ), a circuit member of various surface states of an inorganic material such as cerium oxide (SiO 2 ). The circuit connecting member 1 is made of the adhesive composition of the present invention or a cured film-form adhesive, and the circuit connecting member I 含有 contains an insulating substance π and conductive particles 7 : conductive particles 7 ' It is disposed not only between the opposing circuit electrode 22 and the circuit electrode 32 but also between the main faces 2 1 a and 3 1 a. In the connection structure of the circuit member, the circuit electrodes 22 and 32 are electrically connected via the conductive particles 7, that is, the conductive particles 7 are in direct contact with both of the circuit electrodes 22 and 32. Here, the conductive particles 7 are (e) conductive particles described above, and the insulating material Π is a cured product of the insulating constituents constituting the adhesive composition or the film-like adhesive of the present invention. In the connection structure of the circuit member, since the above-mentioned 'opposite circuit electrode-24-201202377 2 2 and the circuit electrode 3 2 are electrically connected via the conductive particles 7, the circuit electrodes 22 and 32 are sufficiently reduced. Since the resistance is connected, the flow of current between the circuit electrodes 22 and 32 can be smoothly performed, and the function of the circuit can be sufficiently exhibited. Further, when the one circuit connecting member does not contain the conductive particles 7, the circuit electrode 22 and the circuit electrode 32 are brought into direct contact with each other to be electrically connected. Since the circuit connecting member 10 is composed of the adhesive composition of the present invention or the cured product of the film-like adhesive, the connection strength of the circuit connecting member 10 is sufficiently increased for the circuit member 20 or 30, and Even after the reliability test (high temperature and high humidity test), stable performance (adhesive strength and connection resistance) can be maintained.
接著’說明關於上述電路構件之連接構造之製造方法 的其中一例。首先，準備上述之第一電路構件2〇、及薄膜 狀黏著劑（薄膜狀電路連接材料）4 0 (參考圖3 (a))。薄膜狀 電路連接材料40 ’爲將黏著劑組成物（電路連接材料）成形 爲薄膜狀所成者’含有導電性粒子7與黏著劑組成物5。 再者’電路連接材料不含有導電性粒子7時，此電路連接 材料可作爲絕緣性黏著劑使用於各向異導電性黏著，亦特 別柄爲NCP(Non-C〇nductive Paste)。此外，電路連接材料 含有導電性粒子7時，亦稱此電路連接材料爲ACP (Anisotropic Conductive Paste)。 薄膜狀電路連接材料4 0的厚度較佳爲1 0 ~ 5 0 μιπ，薄 膜狀電路連接材料4〇的厚度未達1 〇μηι，則會有電路電極 22、32間電路連接材料塡充不足之傾向，另外，超過 -25- 201202377 5 Ομηι，則會有電路電極22、32間的黏著劑組成物無法完 全排除，電路電極22、32間的導通的確保變難之傾向。 接著，將薄膜狀電路連接材料40，放置於第一電路構 件20之形成電路電極22之面上，再者，薄膜狀電路連接 材料40附著在支持體（未圖示）上時，使薄膜狀電路連接材 料40側，面向著第一電路構件20的情況下放置在第一電 路構件20上。此時，因爲薄膜狀電路連接材料40爲薄膜 狀，故操作容易，因此，可輕易的使薄膜狀電路連接材料 40介於第一電路構件20與第二電路構件3 0之間，而可輕 易的進行第一電路構件20與第二電路構件30的連接操作 〇 然後’在圖3(a)的箭頭Α及Β方向上加壓薄膜狀電路 連接材料4 0 ’將薄膜狀電路連接材料4 0假連接於第一電 路構件2 0 (參照圖3 (b ))，此時’可一邊加熱—邊加壓，惟 ’加熱溫度係不使薄膜狀電路連接材料40中的黏著劑組 成物硬化之溫度’亦即比自由基聚合起始劑產生自由基的 溫度低的溫度。 接著，如圖3(c)所示’將第二電路構件3〇，使第二電 路電路面向著第一電路構件2 0的情況下放置在薄膜狀電 路連接材料40上。再者，薄膜狀電路連接材料4〇附著在 支持體（未圖示）上時，將支特體剥離後使第二電路構件3〇 放置在薄膜狀電路連接材料4〇上。 然後’一邊加熱薄膜狀電路連接材料4〇，一邊在圖 3(c)的箭頭a及β方向上隔著第—及第二電路構件2〇、3〇 -26- 201202377 進行加壓，此時的加熱溫度，爲自由基聚合起始劑可產生 自由基之溫度’藉此，自由基聚合起始劑中產生自由基， 使自由基聚合性化合物開始聚合，像這樣使薄膜狀電路連 接材料40進行硬化處理而進行真正的連接，得到如圖2 所示的電路構件之連接構造。 此處，連接條件如之前所敍述，較佳爲加熱溫度 100〜2 5 0 °c、壓力0_1〜lOMPa'連接時間0_5秒〜120秒， 此等條件可依使用用途、黏著劑組成物、電路構件適當的 選擇，必要時可進行後硬化。 如上述作法製造電路構件之連接構造，所得到的電路 構件之連接構造中，可使導電性粒子7與互相對向的電路 電極22、32雙方接觸，可充分的降低電路電極22、32間 的連接電阻。 此外，藉由薄膜狀電路連接材料40的加熱，在電路 電極2 2與電路電極3 2之間的距離充分變小的狀態下，黏 著劑組成物5硬化後成爲絕緣性物質1 1，第一電路構件 20與第二電路構件30隔著電路連接構件1 〇堅固的連接。 亦即，所得到的電路構件之連接構造中，電路連接構件1 0 ，係由含有上述黏著劑組成物之電路連接材料的硬化物所 構成，故充分的提高對於電路構件20或30之電路連接構 件1 〇的黏著強度，即使在信賴性試驗（高溫高濕試驗）後亦 可維持穩定的性能 再者，上述實施形態，黏著劑組成物5可使用至少含 有藉由加熱產生自由基之自由基聚合起始劑者，亦可使用 -27- 201202377 僅用光照射產生自由基的自由基聚合起始劑取代此自由基 聚合起始劑。此時，薄膜狀電路連接材料40的硬化處理 時’亦可用光照射取代加熱。此外，上述實施形態，係使 用薄膜狀電路連接材料4 0製造電路構件之連接構造，但 亦可使用未形成薄膜狀之電路連接材料取代薄膜狀電路連 接材料4 0，此時亦可使電路連接材料溶解於溶劑，將此溶 液塗佈於第一電路構件2 0或第二電路構件3 〇的其中之一 後乾燥，使第一及第二電路構件2 0、3 0間隔著電路連接 材料。 再者，m路構件之連接構造的製造方法，除了藉由加 熱或光照射產生自由基之自由基聚合起始劑之外，必要時 可使用藉由超音波、電磁波等產生自由基之自由基聚合起 始劑。 【贲施方式】 以下，藉由贲施例更詳細的說明本發明，但本發明並 不拘限於此等實施例。 (苯氧基樹脂溶液的調製） 將40質Μ份之苯氧基樹脂（商品名：PKHM-30， I n C h e m公司製），溶解於6 0質童份的甲基乙基酮中，調 製固體成份40質量％的苯氧基樹脂溶液。 (丁縮醛樹脂溶液的調製） -28 - 201202377 將40質量份之丁縮醛樹脂（商品名：DENKA BUTYRAL3000- 1 -電氣化學工業公司製），溶解於60質量 份的甲基乙基酮中，調製固體成份4 0質量％的丁縮醒樹脂 溶液。 (聚酯尿烷樹脂溶液的準備） 準備U R - 3 2 1 0 (商品名：東洋紡公司製，樹脂份3 0質 量％的甲基乙基酮及甲苯溶解品），作爲聚酯尿烷樹脂。 (尿烷樹脂的合成） 將450質量份之重量平均分子量2000的聚己二酸丁 二醇醋（polybuthylene adipate diol)(Aldrich 公司製）、450 質量份之重量平均分子量 2000 的聚氧四甲二醇 (polyoxytetramethyleneglycol)( Aldrich 公司製）、及 1〇〇 質量份之1,4 -丁二醇（Aldrich公司製），於4000質量份之 甲基乙基酮中均勻的混合，此時加入3 90質量份之二苯基 甲院二異氰酸酯（A1 d r i c h公司製）後得到反應液，以5 〇。〇 使其反應而得到尿烷樹脂，所得到的尿烷樹脂的重量平均 分子量爲1 0萬。 (自由基聚合性化合物的準備） 準備9，9 -雙（4 -經基苯基）荀環氧乙院改性二丙稀酸酯（ 商品名：EA-〇2〇〇、大阪GAS股份有限公司製、E〇鍵的 重複數（式（A)中之k+Ι的値）：2、重量平均分子量： -29- 201202377 546.6 1 )、9,9-雙（4-羥基苯基）芴環氧乙烷改性二丙烯酸酯（ 商品名：E A - 0 5 0 0、大阪g A S股份有限公司製、E 0鏈的 重複數（式（A)中之lc+Ι的値）：5、重量平均分子量： 678.77)、EO改性雙酚a二丙烯酸酯（商品名：FA-324A、 曰立化成工業股份有限公司製）' 及2-(甲基）丙烯醯氧基 磷酸酯（Μ品名：丨i g h t e s t e r P - 2 Μ、共榮社化學股份有限 公司製）。 (尿烷丙烯酸酯的合成） 在具備搅拌機、溫度計、冷卻管及空氣氣體導入管之 反應容器中導入空氣氣體後，裝入2-羥基乙基丙烯酸酯 2 3 8質量份（2.05莫耳）、數平均分子量860的聚（六伸甲基 碳酸酯）二醇（Aldrich公司製）8 60質量份（1莫耳）、氫醌單 甲基醚〇 . 5 3質fi份、二丁茲二月桂酸錫5.5 3質份，於 70〜75 °C加熱，使用3小時均勻滴入異佛爾酮二異氛酸醋 666質量份（3莫耳）後使其反應，經由IR測量確認異瓴酸 酸酯消失時結束反應’得到尿烷丙烯酸酯（UA)，所得到的 尿烷丙烯酸酯的數平均分子量爲3 700。 (自由基聚合起始劑的準備） t-己基過氧化-2-乙基己酸酯（商品名：perhexyl 〇，臼 本油脂股份有限公司製）。 (導電性粒子的製作） -30- 201202377 在以聚苯乙烯爲核的粒子的表面上，設置厚度達到 0.2 μηι的鎳層，此鎳層的外側上設置厚度達到〇.〇2 μηι的金 層’如此作法製作平均粒徑4 μηι及比重2.5的導電性粒子 (實施例1 ~ 6、比較例1〜3 ) 將上述各材料以固形質量比依下述表1所示的比例摻 合，更進一步摻合分散1 . 5體積％ (黏著劑組成物的總體積 基準）的上述導電性粒子而得到黏著劑組成物，將所得到 的黏著劑組成物，使用塗佈裝置塗佈於厚度8 0 μηι的氟樹 脂薄膜上，藉由以70 °C進行1 〇分鐘的熱風乾燥，得到黏 著劑層的厚度爲20μηι的薄膜狀黏著劑。 -31 - 201202377Next, an example of a method of manufacturing the connection structure of the above circuit member will be described. First, the first circuit member 2A and the film-like adhesive (film-like circuit connecting material) 40 described above are prepared (refer to Fig. 3 (a)). The film-like circuit connecting material 40' is formed by forming an adhesive composition (circuit connecting material) into a film shape, and contains conductive particles 7 and an adhesive composition 5. Further, when the circuit connecting material does not contain the conductive particles 7, the circuit connecting material can be used as an insulating adhesive for the isotropic conductive adhesion, and the special handle is NCP (Non-C〇nductive Paste). Further, when the circuit connecting material contains the conductive particles 7, the circuit connecting material is also referred to as ACP (Anisotropic Conductive Paste). The thickness of the film-like circuit connecting material 40 is preferably 10 to 50 μππ, and the thickness of the film-like circuit connecting material 4〇 is less than 1 〇μηι, and the circuit connecting materials between the circuit electrodes 22 and 32 are insufficient. In addition, when the thickness exceeds -25 - 201202377 5 Ομηι, the adhesive composition between the circuit electrodes 22 and 32 cannot be completely eliminated, and the conduction between the circuit electrodes 22 and 32 tends to be difficult. Next, the film-like circuit connecting material 40 is placed on the surface of the first circuit member 20 on which the circuit electrode 22 is formed, and when the film-like circuit connecting material 40 is attached to the support (not shown), the film is formed. The circuit connecting material 40 side is placed on the first circuit member 20 with the first circuit member 20 facing. At this time, since the film-like circuit connecting material 40 is in the form of a film, the operation is easy, and therefore, the film-like circuit connecting material 40 can be easily interposed between the first circuit member 20 and the second circuit member 30, and can be easily Performing a connection operation of the first circuit member 20 and the second circuit member 30, and then pressing the film-like circuit connecting material 40 in the direction of the arrow Α and Β in FIG. 3(a) to connect the film-like circuit to the material 40 False connection to the first circuit member 20 (refer to FIG. 3(b)), at this time 'can be heated while being pressurized, but the heating temperature does not harden the adhesive composition in the film-like circuit connecting material 40. The temperature 'is a temperature lower than the temperature at which the radical polymerization initiator generates radicals. Next, as shown in Fig. 3(c), the second circuit member 3 is placed so that the second circuit circuit faces the first circuit member 20, and is placed on the film-like circuit connecting material 40. Further, when the film-like circuit connecting material 4 is attached to a support (not shown), the support is peeled off and the second circuit member 3 is placed on the film-like circuit connecting material 4A. Then, while heating the film-like circuit connecting material 4, the pressure is applied to the first and second circuit members 2〇, 3〇-26-201202377 in the directions of arrows a and β in Fig. 3(c). The heating temperature is a temperature at which a radical polymerization initiator can generate a radical. Thus, a radical is generated in the radical polymerization initiator, and the radical polymerizable compound starts to polymerize, and the film-like circuit connecting material 40 is thus obtained. The hardening treatment is performed to make a true connection, and the connection structure of the circuit member as shown in Fig. 2 is obtained. Here, the connection conditions are as described above, preferably a heating temperature of 100 to 2 50 ° C, a pressure of 0_1 to 10 MPa, a connection time of 0 to 5 seconds to 120 seconds, and the conditions may be depending on the intended use, the adhesive composition, and the circuit. The components are appropriately selected and post-hardened if necessary. When the connection structure of the circuit member is manufactured as described above, in the connection structure of the obtained circuit member, the conductive particles 7 can be brought into contact with the mutually opposing circuit electrodes 22 and 32, and the circuit electrodes 22 and 32 can be sufficiently reduced. Connect the resistor. Further, in the state where the distance between the circuit electrode 2 2 and the circuit electrode 32 is sufficiently reduced by the heating of the film-like circuit connecting material 40, the adhesive composition 5 is cured to become the insulating material 1 1, first. The circuit member 20 and the second circuit member 30 are firmly connected via the circuit connecting member 1. That is, in the connection structure of the obtained circuit member, the circuit connecting member 10 is composed of a cured material containing the circuit connecting material of the above-described adhesive composition, so that the circuit connection to the circuit member 20 or 30 is sufficiently improved. The adhesive strength of the member 1 can maintain stable performance even after the reliability test (high temperature and high humidity test). In the above embodiment, the adhesive composition 5 can use at least a radical which generates radicals by heating. As the polymerization initiator, the radical polymerization initiator may be substituted only with a radical polymerization initiator which generates a radical by light irradiation using -27 to 201202377. At this time, the film-like circuit connecting material 40 may be subjected to heat treatment instead of heating. Further, in the above embodiment, the connection structure of the circuit member is manufactured using the film-like circuit connecting material 40. However, the film-like circuit connecting material 40 may be replaced with a circuit-connecting material which is not formed in a film shape, and the circuit connection may be made at this time. The material is dissolved in a solvent, and the solution is applied to one of the first circuit member 20 or the second circuit member 3 and dried to separate the first and second circuit members 20, 30 from the circuit connecting material. Further, in the method of manufacturing the connection structure of the m-way member, in addition to the radical polymerization initiator which generates radicals by heating or light irradiation, a radical which generates radicals by ultrasonic waves, electromagnetic waves or the like may be used as necessary. Polymerization initiator. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the embodiments. (Preparation of phenoxy resin solution) A 40-mass phenoxy resin (trade name: PKHM-30, manufactured by I n C hem Co., Ltd.) was dissolved in methyl ethyl ketone of 60 children. A phenoxy resin solution having a solid content of 40% by mass was prepared. (Preparation of butyral resin solution) -28 - 201202377 40 parts by mass of butyral resin (trade name: DENKA BUTYRAL 3000-1 - manufactured by Denki Kagaku Kogyo Co., Ltd.) was dissolved in 60 parts by mass of methyl ethyl ketone. A 40% by mass solid solution of the condensed resin solution was prepared. (Preparation of polyester urethane resin solution) U R - 3 2 1 0 (trade name: manufactured by Toyobo Co., Ltd., resin parts of 30% by mass of methyl ethyl ketone and toluene dissolved product) was prepared as a polyester urethane resin. (Synthesis of urethane resin) 450 parts by mass of polybuthylene adipate diol (manufactured by Aldrich Co., Ltd.) having a weight average molecular weight of 2000, and 450 parts by mass of polyoxytetramethyl urethane having a weight average molecular weight of 2000 Polyoxytetramethyleneglycol (manufactured by Aldrich Co., Ltd.) and 1 part by mass of 1,4-butanediol (manufactured by Aldrich Co., Ltd.) were uniformly mixed in 4000 parts by mass of methyl ethyl ketone, and 3 90 was added at this time. The reaction solution was obtained in an amount of 5 后 after the mass of the diphenyl carbene diisocyanate (manufactured by A1 Drich Co., Ltd.). 〇 The reaction was carried out to obtain a urethane resin, and the obtained urethane resin had a weight average molecular weight of 100,000. (Preparation of radically polymerizable compound) Preparation of 9,9-bis(4-phenylphenyl) oxime epoxy epoxide modified diacrylate (trade name: EA-〇2〇〇, Osaka GAS Limited) Company-made, E〇 bond repeat number (k+Ι in formula (A)): 2. Weight average molecular weight: -29- 201202377 546.6 1 ), 9,9-bis(4-hydroxyphenyl)芴Ethylene oxide modified diacrylate (trade name: EA - 0 5 0 0, manufactured by Osaka g AS Co., Ltd., the number of repetitions of the E 0 chain (the lc + Ι in the formula (A)): 5, Weight average molecular weight: 678.77), EO-modified bisphenol a diacrylate (trade name: FA-324A, manufactured by Toray Chemical Industry Co., Ltd.) and 2-(meth)acryloyloxy phosphate (product name) :丨ightester P - 2 Μ, Kyoeisha Chemical Co., Ltd.). (Synthesis of urethane acrylate) After introducing air gas into a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe, and an air gas introduction pipe, 2 3 parts by mass of 2-hydroxyethyl acrylate (2.05 mol) was charged. Poly(hexamethylene methyl carbonate) diol having a number average molecular weight of 860 (manufactured by Aldrich Co., Ltd.) 8 60 parts by mass (1 mol), hydroquinone monomethyl ether oxime. 5 3 mass parts, dibutz laurel 5.5 parts of acid tin, heated at 70 to 75 ° C, and 6.6 parts by mass (3 moles) of isophorone diisocyanate was added dropwise thereto for 3 hours, and then reacted, and isophthalic acid was confirmed by IR measurement. When the acid ester disappeared, the reaction was terminated to obtain urethane acrylate (UA), and the obtained urethane acrylate had a number average molecular weight of 3,700. (Preparation of a radical polymerization initiator) t-hexylperoxy-2-ethylhexanoate (trade name: perhexyl®, manufactured by Otsuka Oil Co., Ltd.). (Preparation of conductive particles) -30- 201202377 A nickel layer having a thickness of 0.2 μm is provided on the surface of particles having polystyrene as a core, and a gold layer having a thickness of 〇.〇2 μηι is disposed on the outer side of the nickel layer. In this way, conductive particles having an average particle diameter of 4 μηι and a specific gravity of 2.5 were produced (Examples 1 to 6 and Comparative Examples 1 to 3). The above materials were blended in a solid mass ratio according to the ratio shown in Table 1 below. Further, the above-mentioned conductive particles were dispersed and dispersed at 1.5% by volume (based on the total volume of the adhesive composition) to obtain an adhesive composition, and the obtained adhesive composition was applied to a thickness of 80 using a coating device. On the fluororesin film of μηι, a film-like adhesive having a thickness of 20 μm of the adhesive layer was obtained by hot air drying at 70 ° C for 1 Torr. -31 - 201202377
配合劑 G施例1 W施例2 Π施例3 K施例4 Π施例5 K施例6 比較例1 比較例2 比較例3 熱塑性 樹脂 苯铽® 樹脂 40 - 40 • - - - * - 丁縮醛 樹脂 - 35 - 35 * - 35 35 35 聚酯尿 烷樹脂 - - > • 40 40 - - - 尿烷 樹脂 10 15 10 15 10 10 15 15 15 自由基 聚合性 化合物 EA-0200 50 50 30 25 50 . • EA-0500 20 15 40 . 眷 UA • 10 10 50 30 FA-324A • _ 50 20 含磷酸化 合物 P-2M 3 3 3 3 3 3 3 3 3 自由基聚 合起始劑 Peihexyl 0 3 3 3 3 3 3 3 3 3 (摻合的單位爲ϊϊίδ份) [黏著強度、連接電阻的測s ] 使用依上述製法所得到的薄膜狀黏著劑，將具有5 0 0 條之線宽2 5 μΐΏ、間距5 0 μιπ、厚度1 8 μηι的銅電路之可撓 性電路板（F P C基板）、與形成〇 . 2 μηι的氧化銦（I Τ 0)的薄層 之玻璃（ΙΤΟ基板、厚度1 .lmm、表面電阻20 Ω /□.)，使用 熱壓著裝置（加熱方式：熱壓溫度恆定（constant heat)型、 Toray Engineering股份有限公司製），以160 °C溫度用 3MPa進行10秒的加熱加壓，藉此製作將FPC基板與IT0 基板藉由薄膜狀黏著劑的硬化物連接達寬度2mm的連接 -32- 201202377 物（電路構件之連接構造）。 剛黏著完成、與在8 5 °C、8 5 %RH的高溫高濕槽中保 持1 6 8小時後，用萬用錶測量此連接物的相鄰電路間的電 阻値’再者’此電阻値係以相鄰的電路間的電阻3 7點的 平均所表示，結果列示於表2。 此外’此連接物的連接強度，依據JIS-Z023 7之90 度剝離法測量 '評估’此處，黏著強度的測量裝置使用東 洋伯露得股份有限公司製的TENSILON UTM-4(剝離速度 5 0 m m /分鐘、2 5 °C )’再者’關於黏著強度，亦於剛黏著完 成、與在85°C、85%RH的高溫高濕槽中保持168小時後 進行測量，其結果列示於表2。 [表2] 項 0 連接電 阻（Ω ) 黏著強度（N/m) 剛黏著完成 1 6 8小 時後 剛黏著完成 1 6 8小時後 實 施 例 1 1 • 5 2.8 700 620 實 施 例 2 1 .2 2.5 7 10 680 實 施 例 3 1.3 2.3 680 560 實 施 例 4 1.3 2. 4 750 620 實 施 例 5 1 .2 2. 2 7 10 650 實 施 例 6 1.7 2.4 680 5 70 比 較 例 1 2.6 7.8 670 480 比 較 例 2 1 .9 3.2 480 330 比 較 例 3 2 .4 6. 5 520 430 實施例1〜6所得到的薄膜狀電路連接材料，於加熱溫 度1 60°C的連接條件，在剛黏著完成與在8 5 °C、8 5 %RH的 -33- 201202377 高溫高濕槽中保持1 6 8小時後的雙方，皆被確認顯示出優 良的連接電阻及黏著強度，及對於廣域的加熱溫度顯示出 優良的特性》相對於此，未使用本發明之具有芴構造之自 由基聚合性化合物之比較例1〜3的薄膜狀黏著劑，未得到 優良的特性’亦即，確認比較例1的薄膜黏著劑被觀察到 其商溫局濕處理的連接電阻値高，比較例2的薄膜狀黏著 劑被觀察到剛黏著完成及高溫高濕處理後的黏著力低，此 外比較例3的薄膜狀黏著劑被觀察到其高溫高濕處理後的 連接電阻的上昇與黏著力的降低。 [貯藏穩定性的評估] 將If施例1所得到的薄膜黏著劑，在施以真空包裝的 狀態下’於40°C放置3天後，然後，使用此放置後的薄膜 狀黏著劑，與K施例1同樣地將F P C基板與IΤ Ο基板經 由160°C、3MPa、10秒的加熱壓著連接達寬度2mm，製 作連接物（電路構件之連接構造）。將所得到的連接物的剛 黏著完成的黏著強度及黏著電阻，使用與上述實施例1等 相同的方法測Μ時，黏著強度爲7 1 ON /m、連接電阻爲1 . 2 Ω，確認其貯藏穏定性優異。 經由上述，確認依據本發明，可提供雖爲自由基硬化 系’但可得到優異的黏著強度，且即使在信賴性試驗（高 溫高濕試驗）後仍可維持穏定的性能（黏著強度及連接電阻） 之黏著劑組成物、使用其之薄膜狀黏著劑及電路構件之連 接構造。 -34- 201202377 產業上的可利用性 如上述說明，依據本發明，可提供雖爲自由基硬化系 ，但可得到優異的黏著強度，而且在信賴性試驗（例如85 °C /85%RH放置）後亦可維持穩定的性能（黏著強度及連接 電阻）之黏著劑組成物及電路構件之連接構造。 【圖式簡單說明】 [圖1 ]表示由本發明的黏著劑組成物所成的薄膜狀黏 著劑的其中之一實施形態之截面圖。 [圖2]表示本發明的電路構件之連接構造的其中之一 的實施形態之槪略截面圖。 [圖3] (a)〜（c)爲連接各電路構件之一連串的步驟圖。 【主要元件符號說明】 1 :薄膜狀黏著劑、5 :黏著劑成份、7 :導電性粒子 、：1 〇 :電路連接構件、1 1 :絕緣性物質、2 0 :第一電路構 件、21:電路基板（第一電路基板）、21a:主面、22:電路 電極（第一電路電極）、30:第二電路構件、31:電路基板（ 第二電路基板）、31a:主面、32:電路電極（第二電路電極 )、40 :薄膜狀電路連接材料。 -35-Formulation G Example 1 W Example 2 Π Example 3 K Example 4 Π Example 5 K Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Thermoplastic Resin Benzene® Resin 40 - 40 • - - - * - Butyral Resin - 35 - 35 * - 35 35 35 Polyester Urethane Resin - - > • 40 40 - - - Urethane Resin 10 15 10 15 10 10 15 15 15 Radical Polymerizable Compound EA-0200 50 50 30 25 50 . • EA-0500 20 15 40 . 眷UA • 10 10 50 30 FA-324A • _ 50 20 Phosphate-containing compound P-2M 3 3 3 3 3 3 3 3 3 Free radical polymerization initiator Peihexyl 0 3 3 3 3 3 3 3 3 3 (The unit of blending is ϊϊίδ parts) [Measurement of adhesion strength and connection resistance s] Using the film-like adhesive obtained by the above method, there will be a line width of 500 lines 2 5 A flexible circuit board (FPC substrate) of a copper circuit having a pitch of 5 0 μππ, a thickness of 18 μm, and a thin layer of indium oxide (I Τ 0) forming 〇. 2 μηι (ΙΤΟ substrate, thickness 1 .lmm, surface resistance 20 Ω / □.), using a hot pressing device (heating method: constant heat type, Toray Engineerin G Co., Ltd.), by heating and pressurizing at a temperature of 160 °C for 3 seconds at 3 MPa, thereby making a connection between the FPC substrate and the IT0 substrate by a cured product of a film-like adhesive to a width of 2 mm - 32 - 201202377 Object (connection structure of circuit components). After the adhesion is completed and maintained for 168 hours in a high-temperature and high-humidity tank at 85 ° C and 85 % RH, the resistance between adjacent circuits of the connector is measured with a multimeter 再 'again' the resistance system The results are shown by the average of the resistances of 7 7 points between adjacent circuits, and the results are shown in Table 2. In addition, the connection strength of this connector is measured according to the 90 degree peeling method of JIS-Z023 7. Here, the adhesion strength measuring device uses TENSILON UTM-4 manufactured by Toyo Bolu Co., Ltd. (peeling speed 50) Mm / min, 2 5 ° C ) 'again' about the adhesion strength, also measured after the adhesion is completed, and maintained in the high temperature and high humidity tank at 85 ° C, 85% RH for 168 hours, the results are listed in Table 2. [Table 2] Item 0 Connection resistance (Ω) Adhesion strength (N/m) Just after adhesion is completed 1 6 8 hours After adhesion is completed 1 6 8 hours Example 1 1 • 5 2.8 700 620 Example 2 1 .2 2.5 7 10 680 Example 3 1.3 2.3 680 560 Example 4 1.3 2. 4 750 620 Example 5 1 .2 2. 2 7 10 650 Example 6 1.7 2.4 680 5 70 Comparative Example 1 2.6 7.8 670 480 Comparative Example 2 1 .9 3.2 480 330 Comparative Example 3 2 .4 6. 5 520 430 The film-like circuit connecting materials obtained in Examples 1 to 6 were joined at a heating temperature of 1 60 ° C, and the bonding was completed at 8 5 °. C, 8 5 % RH -33 - 201202377 Both sides after 168 hours in the high temperature and high humidity chamber were confirmed to exhibit excellent connection resistance and adhesion strength, and showed excellent characteristics for wide-area heating temperature. In contrast, in the film-like adhesives of Comparative Examples 1 to 3 in which the radically polymerizable compound having a fluorene structure of the present invention was not used, excellent characteristics were not obtained, that is, the film adhesive of Comparative Example 1 was observed. The connection resistance to the wet treatment of the commercial temperature bureau is high, The film-like adhesive of Example 2 was observed to have low adhesion after completion of the adhesion and high-temperature and high-humidity treatment, and the film-like adhesive of Comparative Example 3 was observed to have an increase in the connection resistance and adhesion after the high-temperature and high-humidity treatment. The reduction. [Evaluation of Storage Stability] The film adhesive obtained in Example 1 was placed in a vacuum package for 3 days at 40 ° C, and then the film adhesive was placed, and In the same manner as in Example 1, the FPC substrate and the I Τ substrate were connected by heating at 160 ° C, 3 MPa, and 10 seconds to a width of 2 mm to fabricate a connector (connection structure of circuit members). When the adhesive strength and the adhesive resistance of the obtained bonded material were measured by the same method as in the above-mentioned Example 1, the adhesive strength was 7 1 ON /m, and the connection resistance was 1.2 Ω, and it was confirmed. Excellent storage stability. From the above, it was confirmed that according to the present invention, it is possible to provide a free radical curing system, but excellent adhesion strength can be obtained, and the performance (adhesive strength and connection) can be maintained even after the reliability test (high temperature and high humidity test). The adhesive composition of the resistor), the film-like adhesive using the same, and the connection structure of the circuit member. -34- 201202377 INDUSTRIAL APPLICABILITY As described above, according to the present invention, although it is a radical curing system, excellent adhesion strength can be obtained, and in a reliability test (for example, 85 ° C / 85% RH placement) After that, it is also possible to maintain a stable performance (adhesion strength and connection resistance) of the adhesive composition and the connection structure of the circuit member. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a film-like adhesive formed of the adhesive composition of the present invention. Fig. 2 is a schematic cross-sectional view showing an embodiment of one of the connection structures of the circuit members of the present invention. [Fig. 3] (a) to (c) are step diagrams for connecting a series of circuit members. [Explanation of main component symbols] 1 : Film adhesive, 5: Adhesive component, 7 : Conductive particles, 1 〇: circuit connecting member, 1 1 : insulating material, 20: first circuit member, 21: Circuit board (first circuit board), 21a: main surface, 22: circuit electrode (first circuit electrode), 30: second circuit member, 31: circuit board (second circuit board), 31a: main surface, 32: Circuit electrode (second circuit electrode), 40: film-like circuit connecting material. -35-